US3294851A - Separation of primary and secondary hydrocarbon chlorides - Google Patents

Separation of primary and secondary hydrocarbon chlorides Download PDF

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Publication number
US3294851A
US3294851A US361223A US36122364A US3294851A US 3294851 A US3294851 A US 3294851A US 361223 A US361223 A US 361223A US 36122364 A US36122364 A US 36122364A US 3294851 A US3294851 A US 3294851A
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US
United States
Prior art keywords
primary
chlorides
dialkylamine
mixture
chloride
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
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US361223A
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English (en)
Inventor
Norman R Roobol
Rupert C Morris
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Shell USA Inc
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Shell Oil Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shell Oil Co filed Critical Shell Oil Co
Priority to US361223A priority Critical patent/US3294851A/en
Priority to BE660375D priority patent/BE660375A/fr
Priority to NL6502449A priority patent/NL6502449A/xx
Priority to FR7133A priority patent/FR1430476A/fr
Priority to FR13815A priority patent/FR1433699A/fr
Priority to GB16534/65A priority patent/GB1084807A/en
Priority to DE19651493043 priority patent/DE1493043A1/de
Priority to BE662768A priority patent/BE662768A/xx
Priority to NL6504952A priority patent/NL6504952A/xx
Priority to CH544865A priority patent/CH461449A/de
Application granted granted Critical
Publication of US3294851A publication Critical patent/US3294851A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C291/00—Compounds containing carbon and nitrogen and having functional groups not covered by groups C07C201/00 - C07C281/00
    • C07C291/02—Compounds containing carbon and nitrogen and having functional groups not covered by groups C07C201/00 - C07C281/00 containing nitrogen-oxide bonds
    • C07C291/04—Compounds containing carbon and nitrogen and having functional groups not covered by groups C07C201/00 - C07C281/00 containing nitrogen-oxide bonds containing amino-oxide bonds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/75—Amino oxides

Definitions

  • Chlorinated higher aliphatic hydrocarbons are useful in the preparation of olefinic hydrocarbons, important uses of which are in the manufacture of higher alcohols and alkylaromatics.
  • hydrocarbon chlorides are prepared by well known methods of substitutive chlorination of aliphatic hydrocarbons.
  • the reaction products obtained in the chlorination of essentially normal paraflins are mixtures of primary and secondary chlorides with the secondary chlorides usually accounting for the major amount of the mixture. Often up to 85% or more of the resulting chlorides may be secondary.
  • the hydrocarbon chlorides are then dehydrochlorinated.
  • the primary chlorides are quite resistant to dehydrochlorination and up to 50% or more of the primary chlorides may not be converted under the usual conditions; more drastic conditiOns result in undesirable side reactions.
  • the unconverted chlorides remain behind in the distillation bottoms mixture, from which separation of the valuable primary chlorides is difficult and costly.
  • the hydrocarbon dehydrochlorination process normally, thus, results in the loss of a significant amount of the valuable primary hydrocarbon chlorides. Steps taken to physically separate the primary and secondary chlorides from one another after the chlorination step and/ or in the distillation bottoms mixture are impractical due to the similarity in physical properties such as boiling points, etc.
  • primary and secondary higher paraflin hydrocarbon chlorides may be separated from mixtures thereof by treating the mixture with a dialkyl amine wherein each alkyl group contains from one to four carbon atoms, whereby the primary chlorides are selectively converted to corresponding tertiary amines and their hydrochloride salts which are separable by aqueous extraction as the salts thereof from the secondary chlorides.
  • the hydrocarbon materials from which the chlorides are prepared are saturated aliphatic hydrocarbons containing from to 30 carbon atoms and mixtures thereof. Especially useful are parafiins having from 12 to 20 carbon atoms from which the corresponding primary and secondary alkyl chlorides are obtained.
  • chloride mixtures which will be treated according to the invention are mixtures of primary and secondary chlorides of decane, undecane, dodecane, tridecane, tetradecane, penta- "ice decane, etc., and mixtures thereof.
  • specific mixtures of aliphatic hydrocarbon chlorides which may be treated comprise for example l-chlorodecane and 3- chlorodecane, l-chlorododecane and 2-chlorododecane and the like.
  • the mixtures may contain alkyl chlorides, such as, for example, l-chlorodecane and 2-chlorododecane or l-chlorotridecane and 3-chlorodecane, etc.
  • the mixtures may be mixtures of, e.g., C secondary and primary alkyl chlorides, C secondary and primary alkyl-chlorides, etc.
  • the amines used to treat the hydrocarbon chloride mixtures are dihydrocarbyl-amines, preferably dialkylamines, having up to 8 carbon atoms. These amines may be represented by the formula RIRZNH wherein R and R are hydrocar-byls, preferably alkyls, of from one to four carbon atoms.
  • R and R are hydrocar-byls, preferably alkyls, of from one to four carbon atoms.
  • the amines where R and R are alike are especially useful, but the alkyls can be diiferent.
  • the amines used in this process include dimethylamine, diethylamine, dipropylarnine, dibutylamine, methylethylamine, diallylamine, methylallylamine, dimethallylamine and dicrotylamines. Dimethylamine is preferred.
  • the method of this invention whereby primary chlorides are separated from secondary chlorides is accomplished by merely heating the dialkylamine with a composition containing a mixture of the chlorides, and separating the resulting tertiary amines of the primary chlorides from the unchanged secondary chlorides.
  • the primary higher alkyl chlorides (RC1) will react with the dialkyl amine (R R NH) to form the corresponding trialkyl tertiary amine, RR R N, which may be present as the hydrochloride salt, RR R N HCl.
  • the secondary or internal higher alkyl chlorides of the mixture are substantially unreactive with the dialkylamines under the process conditions and remain in the mixture unchanged.
  • the tertiary amine may be then separated from the reaction mixture by any suitable means, a particularly useful method being extraction as the hydrochloride salt in aqueous hydrochloric acid.
  • the method according to this invention may be accomplished at various temperatures.
  • the temperature may be from about 20 C. to about 350 C. and preferably between about C. and about 225 C.
  • the secondary hydrocarbon chlorides are dehydrohalogenated to olefins.
  • the hydrogen chloride which is correspondingly released as a result of this thermal dehydrohalogenation reaction adds to the dialkylamine present to form the corresponding dialkylamine hydrogen chloride, thus interfering somewhat with reaction of the primary chloride with the secondary amine.
  • Pressure within the reaction zone may be atmospheric, subatmospheric or superatmospheric.
  • the dialkylamine In a closed reaction vessel the dialkylamine will build up vapor pressure where the reaction temperature is above its boiling point and at higher temperatures a closed reaction vessel is preferred.
  • the maximum pressure buildup within the closed reaction zone will be about 200 p.s.i.g. at temperatures below about 225 C.
  • the dialkylamine may be charged in liquid form or injected under pressure as a gas to a reaction vessel containing the mixture of primary and secondary hydrocarbon chlorides.
  • the reaction vessel may be equipped with a means of stirring or otherwise agitating the reaction mixture.
  • the product mixture may be cooled and filtered to remove any solid material formed such as dialkylamine hydrochloride.
  • the tertiary amine may then be separated from the secondary hydrocarbon chloride (or olefin) by a convenient method such as adding dilute hydrochloric acid to the reaction mixture.
  • the tertiary amine is soluble in the aqueous hydrochloric acid while the hydrocarbon chloride or olefin material is not soluble.
  • the tertiary amine is recoverable as such from the aqueous extract merely by alkalizing with caustic soda or ammonia and phase separating the released water insoluble tertiary amine and the aqueous phase.
  • the tertiary amine products are valuable materials which have a number of important uses, for example, as surface active agents. They are especially useful in the direct preparation of tertiary amine oxides which are used in detergent compositions as foaming and emulsifying agents.
  • the amount of dialkylamine should, in general, be at least the mole equivalent of the amount of primary chloride present. However, during the process, for every mole of dialkylamine, reacted with a mole of primary chloride, there is given oif a mole of hydrogen chloride. Since a portion of this free hydrogen chloride may form an insoluble salt with a portion of the dialkylamine and reduce its availability for reaction with the primary chloride, the use of a larger proportion of dialkylamine is advantageous; an amount of dialkylamine at least equal to twice the molecular equivalent of primary chloride is preferred.
  • the preferred mole ratio of dialkylamine to primary hydrocarbon chlorides is between about 2:1 and 60:1.
  • dialkylamine Larger amounts of the dialkylamine may be used but as a practical matter are not necessary. It has been found that the reaction will proceed more directly and efficiently where substantial molar excess of dialkylamine is used, the excess of dialkylamine providing an excellent solvent medium for the reaction.
  • reaction may be carried out in a common organic solvent which is relatively inert and will not interfere with the reaction such as, for example, alcohols, tetrahydrofuran, dioxane and liquid aliphatic and/ or aromatic hydrocarbons.
  • a common organic solvent which is relatively inert and will not interfere with the reaction such as, for example, alcohols, tetrahydrofuran, dioxane and liquid aliphatic and/ or aromatic hydrocarbons.
  • Example I 57 grams (0.28 mole) of a mixture of monochlorinated dodecanes containing about 16.6% of l-chlorododecane was placed into a one liter stainless steel autoclave equipped with a mechanical stirrer. 100 grams of 'dimethylamine (2.27 mole) was added to the reaction vessel which was then closed and heated to 200 C. Stirring was initiated and the temperature was maintained while the reaction was allowed to proceed for about 5 hours. The reaction vessel was then allowed to cool to room temperature and the excess dimethylamine was removed 'by vaporization. The product was then filtered to remove solid material. To the liquid mixture was then added dilute hydrochloric acid and the mixture well mixed to insure complete solution of the tertiary alkyl amine.
  • the separated hydrochloric acid layer was then neutralized with ammonium hydroxide liberating the dimethyldodecylamine. Analysis of the separated products and a material balance showed that all of the primary alkyl chloride had been converted to tertiary amines while essentially none of the secondary chloride had reacted.
  • Example I A one liter stirred autoclave was charged with 174 grams of C dehydrochlorination bottoms (from dehydrochlorination of monochlorinated C -parafiin) containing a mixture of primary-and secondary C chlorides (43.4% primary C chloride) and 156 grams of dimethylamine and heated slowly from 20 to 200 C. in 4 hours. The temperature was maintained for 1 hour after which time the reaction was allowed to cool to room temperature. The excess dimethylamine was distilled off and the liquid residue filtered and added to 600 ml. of 3 N HCl with stirring. The acid insoluble layer (47.9 grams) was separated and the acid solution neutralized with ammonia. weighed 85.0 grams. Conversion of the primary C chlorides was 100% while none of the secondary chlorides were converted.
  • Example III 50.0 grams of a mixture of monochlorinated dodecane (0.245 mole) having 16.6% of l-chlorododecane was sealed in a glass tube with 100 grams (2.27 moles) of dimethylamine for one week at 22 to 24 C. The excess dimethylamine was then distilled off and the residual liquid was filtered to separate crystals of dimethylamine hydrochloride. The filtrate was stirred into 400 ml. of 3 N HCl and the acid insoluble material separated. The aqueous acid solution was neutralized with ammonia to liberate the tertiary amine. 7.8 grams of dodecyldimethylamine was obtained which was 94% of the theoretical amount based on the amount of l-chlorododecane in the charge.
  • Example IV 115 grams of bottoms obtained from a dehydrochlorination process containing 43.4% primary C chloride and 45 grams of dimethylamine were heated at 200 C. in a stirred autoclave for 5% hours. The reaction vessel was then allowed to cool to room temperature after which the product was treated as described in Example II. Analysis showed that about of the primary C chloride had been converted to the tertiary amine while the secondary chlorides had not reacted.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US361223A 1964-02-28 1964-04-20 Separation of primary and secondary hydrocarbon chlorides Expired - Lifetime US3294851A (en)

Priority Applications (10)

Application Number Priority Date Filing Date Title
US361223A US3294851A (en) 1964-04-20 1964-04-20 Separation of primary and secondary hydrocarbon chlorides
NL6502449A NL6502449A (de) 1964-02-28 1965-02-26
FR7133A FR1430476A (fr) 1964-02-28 1965-02-26 Nouveaux oxydes d'amines tertiaires et préparation d'amines tertiaires correspondantes et facilement transformables en ces nouveaux oxydes d'amines tertiaires
BE660375D BE660375A (de) 1964-02-28 1965-02-26
FR13815A FR1433699A (fr) 1964-04-20 1965-04-20 Séparation d'halogénures d'alcoyles primaires et secondaires
GB16534/65A GB1084807A (en) 1964-04-20 1965-04-20 Separation of primary and secondary alkyl halides
DE19651493043 DE1493043A1 (de) 1964-04-20 1965-04-20 Verfahren zur Trennung primaerer und sekundaerer Alkylhalogenide
BE662768A BE662768A (de) 1964-04-20 1965-04-20
NL6504952A NL6504952A (de) 1964-04-20 1965-04-20
CH544865A CH461449A (de) 1964-04-20 1965-04-20 Verfahren zur Trennung primärer und sekundärer Alkylhalogenide

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US361223A US3294851A (en) 1964-04-20 1964-04-20 Separation of primary and secondary hydrocarbon chlorides

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US361223A Expired - Lifetime US3294851A (en) 1964-02-28 1964-04-20 Separation of primary and secondary hydrocarbon chlorides

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US (1) US3294851A (de)
BE (1) BE662768A (de)
CH (1) CH461449A (de)
DE (1) DE1493043A1 (de)
FR (1) FR1433699A (de)
GB (1) GB1084807A (de)
NL (1) NL6504952A (de)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3371118A (en) * 1964-05-08 1968-02-27 Continental Oil Co Amination process for aliphatic tertiary amines
US3968177A (en) * 1973-09-19 1976-07-06 Chemische Werke Huls Aktiengesellschaft Method for preparing straight-chain primary alcohols
US4024189A (en) * 1975-06-02 1977-05-17 Ethyl Corporation Chemical process
US4358627A (en) * 1980-01-28 1982-11-09 International Business Machines Corporation Reducing chloride concentration
US5347053A (en) * 1992-11-04 1994-09-13 Albemarle Corporation Process for preparing alkylamines

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2006058A (en) * 1931-05-14 1935-06-25 Sharples Solvents Corp Process of making amines and diamines and products of said process
US2349752A (en) * 1940-11-22 1944-05-23 Pittsburgh Plate Glass Co Treatment of allyl type halides
US2448910A (en) * 1944-03-27 1948-09-07 Shell Dev Chlorinated paraffin wax amines for controlling fungi and bacteria
US2569984A (en) * 1951-10-02 Extractive crystallization process
US3223734A (en) * 1961-04-26 1965-12-14 Archer Daniels Midland Co Process for producing tertiary amines

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2569984A (en) * 1951-10-02 Extractive crystallization process
US2006058A (en) * 1931-05-14 1935-06-25 Sharples Solvents Corp Process of making amines and diamines and products of said process
US2349752A (en) * 1940-11-22 1944-05-23 Pittsburgh Plate Glass Co Treatment of allyl type halides
US2448910A (en) * 1944-03-27 1948-09-07 Shell Dev Chlorinated paraffin wax amines for controlling fungi and bacteria
US3223734A (en) * 1961-04-26 1965-12-14 Archer Daniels Midland Co Process for producing tertiary amines

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3371118A (en) * 1964-05-08 1968-02-27 Continental Oil Co Amination process for aliphatic tertiary amines
US3968177A (en) * 1973-09-19 1976-07-06 Chemische Werke Huls Aktiengesellschaft Method for preparing straight-chain primary alcohols
US4024189A (en) * 1975-06-02 1977-05-17 Ethyl Corporation Chemical process
US4358627A (en) * 1980-01-28 1982-11-09 International Business Machines Corporation Reducing chloride concentration
US5347053A (en) * 1992-11-04 1994-09-13 Albemarle Corporation Process for preparing alkylamines

Also Published As

Publication number Publication date
BE662768A (de) 1965-10-20
FR1433699A (fr) 1966-04-01
CH461449A (de) 1968-08-31
NL6504952A (de) 1965-10-21
GB1084807A (en) 1967-09-27
DE1493043A1 (de) 1968-12-19

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